Method for the preparation of terpene ethers



Patented Nov. 5, 19 40 un -TE STATES" Mm'non non THE PREPARATION OF Tanrm ETHERS Donald H. Sheflield, Brunswick, Ga., assignor 'to Hercules Powder Company, Wilmington, Del., a corporation of Delaware No Drawing.

Original application February 15,

1936, Serial No. 64,169. Divided and this application May 20,1939, Serial N- 274,698

This invention relates a method for the production of ethers of terpene compounds and to the product thereof. Moreparticularly, it relates to a method for the production of terpene ethers 5 by the addition of an alcohol at the double bond of an unsaturated terpene compound.

The ethyl ether of camphene has been produced heretofore by the reaction of ethyl alcohol I with the complex cyclic terpene, camphene, in the presence of sulfuric acid as a catalyst. Thus, Semmler (Ber.'33 pp, 3420-32) produced such a compound by boiling a mixture of camphene, ethyl alcohol and sulfuric acid under reflux for several hours. He, likewise, succeeded in producing the ethyl ethers of nopinene and sabinene, but was entirely unsuccessful in producing the ethyl ether of the monocyclic terpene, limonene. Neither polyhydric alcohols, nor monohydric alcohols containing three or more carbon atoms, have been used to produce such ethers heretofore. Now, I have found that I can produce ethers of complex cyclic or of monocyclic terpene-coinpounds with monohydric alcohols containing more than two carbon atoms. Further, by this method I can produce the lower aliphatic ethers of terpenes which have been known heretofore in much higher yields then obtained heretofore in their production. Likewise, I can produce ethers of terpenes from which ethers could not be produced heretofore; due to the instability of the terpene compound.

The method in accordance with this invention consists of reacting an unsaturated terpene compound with an appropriate alcohol in the presence of a suitable catalyst and at a temperature within the range of about C. to about 60 C. The reaction produced by this'method appears to involve the addition of the acid catalyst to a double bond of the unsaturated terpene, to pro- 40 duce an unstable intermediate compound which reacts with the alcohol to produce an ether. Either a mono-ether or a di-ether of the terpene may be produced, as desired, by altering the relative proportions oi the reactants and the conditions of the reaction, so that one Or two double bonds of the terpene compound reacts. When reacting a polyhydrlc alcohol, ethers can be produced in which two or more terpene molecules may be linked in one ether molecule.

Suitable catalysts for this reaction include inorganic acids, such as sulfuric acid and phosphoric acid. or the organic substituted inorganic acids of sulfur, such as, for example, methyl sulfuric acid, phenol sulfonic acid, benzene sulfonic acid; p-toluene sulfonic acid, etc., as more fully drogenated abietyl alcohol, pimarol, hydropimadisclosed in the copending application of Irvin W. Humphrey, Serial No. 67,704 dated March '7, .1936. The concentration of catalyst used in the reaction may be varied over a wide range. Thus, the amount of catalyst used, calculated as sulfuric 5 acid, may be within about the range of 0.1% to 50.0% of the weight of aliphatic .alcoholcon- I tained in the reaction mixture, and will preferably be within the range of 15% to 25%.

saturated monocyclic terpene compound such as, for example, dipentenerterpinene, terpinolene, alpha terpineol, beta terpineol, or mixtures thereof; it may be an unsaturated complex cyclic terpene capable of isomerization to an unsaturated monocyclic terpene compound, which may be, for example, alpha pinene; or it may be a bicyclic terpene which is n'otisomerized under the conditions of the reaction such as, for example, nopinene, camphene and bornylene.

These terpene compounds need not be in the form of pure compounds to be treated in accordance with this invention, but may be reacted in crude form. Thus, in place of the several pure terpene compounds, crude natural mixtures of terpene compounds as, for example, turpentine, pine oil,'etc;, or mixtures of terpenes with petroleum or other saturated hydrocarbons may be used. Various fractions from these mixtures may also be used without the necessityof isolating the compounds in their pure state.

The alcohol used in'this reaction may be a monohydric alcohol such as, for example, methyl 35 alcohol, ethyl alcohol, secondary butyl alcohol, amyl alcohol, ethylene chlorohydrin, tetra-hydrofurfuryl alcohol, benzyl alcohol, stearyl alcohol, lauryl alcohol, oleyl alcohol, abietyl alcohol, hy-

rol, etc., or mixtures thereof. Alternately, it may be a polyhydric alcohol such as, for example,

ethylene glycol, diethylene glycol, glycerol, etc.

The alcohol employed in the reaction will preferably be anhydrous, or substantially so. 45

The relative proportions of the aliphatic alcohol and the terpene compound used in the reaction mixture will depend on the molecular weight of the aliphatic alcohol. To obtain the highest yields of the terpene ether, it is desirable to use not less than one and one-half moles, and preferably at least three moles of the aliphatic alcohol per mole of the terpene compound.

The procedure for the production of aliphatic ethers of the unsaturated monocyclic terpenes in distilled over caustic in vacuo.

accordance with this invention is illustrated by the following examples:

Example 1 Example 2 2500 parts by volume of alpha terpineol was mixed with 1500 parts by volume of a methyl alcohol-sulfuric acid solution containing 15-25% sulfuric acid, to produce a homogeneous solution. This solution was then warmed to 25-40" C. and held at this temperature with agitation for a period of twelve hours. The reaction mixture was then washed with water, and then steam The steam distilled product was then fractionated to give four fractions, which gave analyses as follows: First fractiondipentene, terpinene, terpinoleneyield 10-15%. Second fraction-terpinyl methyl etheryield 10-15%. Third fractionterpineol (unreacted)-yield 25-30%. Fourth fraction 1,8-di-methoxymenthane and l-methoxymenthane-8-ol-yield 35-50%. The fourth out had 'boils at 230-232 C. and l-methoxymenthane-8- ol boils at 244-246 C. under atmospheric pressure.

Example 3 2000 grams of alpha-pinene were added to 2000 grams of methanol containing 10% sulfuric acid by weight, while cooling externally with water. The reaction is exothermic, hence the pinene was added at such a rate as would allow a maximum temperature of the reaction mixture of 50 0. Thirty minutes were required for the complete addition of the pinene. The mixture was then agitated for an additional three hours, and the oil layer allowed to separate. This layer was then recovered, washed with caustic soda, and then distilled in vacuo. The yield was about 2400 grams of a crude ether mixture, which was 843-. proximately 50% terpinyl methyl ether having a boiling point of 212-214 C. The remaining 50% was a mixture of 1,8-dimethoxymenthane boiling at 228-232" C. and bornylmethyl ether boiling at192-193 0.

Example 4 bicyclic alpha-pinene to a mono-cyclic terpinyl form. The temperature of the reaction mixture was held by cooling to a maximum of 45 C., with continued agitation for a period of about three hours. The oily layer was then allowed to separate and removed from the reaction mixture. It was then washed with water and frac- Il tionated. over caustic in vacuo. Fractionation A" H 1%; r

oi this crude product gave two cuts. One of these fractions was composed of a mixture of dipentene, terpinene, terpinoiene, and made up about 30 of the yield on the basis of the original turpentine. The other fraction was a mixture of terpene ethers including terpinylmethyl ether, 1,8-dimethoxymenthane and bornylmethyl ether.

Example 5 A mixture of isopropyl terpene ethers was prepared from wood turpentine following the procedure of Example 4, except with the substitution of 3500 parts of isopropyl alcohol for the 2400 partsof methanol usedin that example.

Example 6 500 cc. of alpha-pinene, 500 cc. of butyl alcohol and 25 cc. of methyl sulfuric acid were agitated at 40-60 C. for five hours. The product was then washed with water and then distilled over caustic in'vacuo to obtain the following fractions:

(A) 'Butyl alcohol.

(B) Dipentene, terpinene, terpinolene' mixture.

(C) Terpinyl butyl ether cut (300 cc.) B. P. 230-250 C.

(D) A small residue of about 5%.

Example 7 100 grams of methanol, 10 cc. of phenol sul-' fonic acid and 1000 cc. of dipentene were refluxed for a period of 7 hours. The mixture was then cooled, the oily layer separated and washed with water. The oily layer was then fractionated over caustic in vacuo to obtain the following fractions:

(A) A mixture of dipentene, terpinene, terpinolene.

(B) Terpinyl methyl ether containing a small amount of 1,8-di-methoxymenthane. The yield of this fraction was 90% on the basis of the dipentene used.

It will be understood that the details and examples hereinbefore set forth are illustrative only, and that the invention herein broadly described and claimed is in no way limited thereby.

The aliphatic ethers of terpene compounds produced in accordance with this invention are useful as solvents and plasticizers in protective coatings and in printing inks. I

' No claim is made herein for a process involving the use of an organic substituted inorganic acid as catalyst for the production of terpene ethers, since such forms the subject of the copending application of Irvin W. Humphrey, Serial No. 67,704 flled March 7, 1936, which has been issued as U. S. Patent 2,136,011.

This is a division of my application Serial No. 64,169 for an improvement in the Method for the preparation of terpene ethers, which was filed February 15, 1936.

What I claim and desire to protest by Letters Patent is:

1. The. method of producing a terpene ether which includes reacting an unsaturated terpene compound with a polyhydric alcohol in the presence of an acidic catalyst at a temperature within the range of about 30 .C. to about 60 C.

2. Themethod of producing a terpene ether which includes reacting an unsaturated terpene hydrocarbon with a polyhydric alcohol in the presence of an acidic catalyst at a temperature within the range 01' about 30 C. to about 60 C.

3. The method of producing a terpene ether which includes reacting pinene with a polyhydric alcohol in the presence of an acidic catalyst at a temperature within the range oi about 30 C. to about 60 C.

4. The method of producing a terpene ether which includes reacting pinene with a glycol in the presence of an acidic.catalyst at a temperature within the range of about 30 C. to about 60 C. j I

'7. The method of producing a terpene ether which includes reacting pinene with ethylene glycol in the presence of an acidic catalyst at a temperature within the range of about 30 C. to about 60 C.

8."l'he method of producing a terpene ether which includes reacting pinene with ethylene glycol in the presence of sulfuric acid at a temperature within the range of about 30 C. to about 60 C.

9. The method of producing a terpene ether which includes reacting pinene with diethyleneglycol in the presence .of an acidic catalyst at a temperature within the range of about 30 C. to about 60 C.

10. The method of producing a terpene ether which includes reacting pinene with diethyleneglycol in the presence of sulfuric acid at a temperature within the rangeof about 30 C. to about 60 C. v

I DONALD H. SHEFFIELD; 

